The direct synthesis of 6-amino-6-deoxyaldonic acids as monomers for the preparation of polyhydroxylated nylon 6

6-Azido-6-deoxy-d-galactitol and d-mannitol were obtained quantitatively via the reduction of the corresponding 6-azido-6-deoxy-d-hexono-1,4-lactones, and 6-azido-6-deoxy-d-glucitol was obtained by the reduction of 6-azido-6-deoxyglucose in good yields. The reduction of monoazidodeoxyhexitols by catalytic hydrogenation gave the monoaminohexitol analogues in 95–98% yields. Oxidation of these afforded the corresponding 6-amino-6-deoxy-d-aldonic acids in moderate yields. Alternatively, saponification of 6-azido-6-deoxy-d-hexonolactones gave 6-azido-6-deoxyaldonic acid salts which, after reduction followed by neutralization, led to the expected compounds in 82–88% overall yields.

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6-Azido-6-deoxy-d-galactitolC6H13N3O5Ee = 100%[α]D24=-15.4 (c 0.5, DMSO)Source of chirality: d-galactono-1,4-lactone

6-Azido-6-deoxy-d-mannitolC6H13N3O5Ee = 100%[α]D24=+27 (c 1.0, H2O)Source of chirality: d-mannono-1,4-lactone

6-Azido-6-deoxy-d-glucitolC6H13N3O5Ee = 100%[α]D24=+12.2 (c 0.5, H2O)Source of chirality: d-glucose

6-Amino-6-deoxy-d-galactitolC6H15O5NEe = 100%[α]D24=+22 (c 0.8, H2O)Source of chirality: d-galactono-1,4-lactone

6-Amino-6-deoxy-d-mannitolC6H15O5NEe = 100%[α]D24=+28.4 (c 1.0, H2O)Source of chirality: d-mannono-1,4-lactone

6-Amino-6-deoxy-d-glucitolC6H15O5NEe = 100%[α]D24=+4.2 (c 1.0, H2O)Source of chirality: d-glucose

6-Azido-6-deoxy-d-glucono-1,5-lactoneC6H9N3O5Ee = 100%[α]D24=+79 (c 0.5, MeOH)Source of chirality: d-glucono-1,5-lactone

6-Azido-6-deoxy-d-galactonic acid sodium saltC6H10N3NaO6Ee = 100%[α]D24=+64.7 (c 0.4, H2O)Source of chirality: d-galactono-1,4-lactone

6-Azido-6-deoxy-d-mannonic acid sodium saltC6H10N3NaO6Ee = 100%[α]D24=+5.1 (c 0.6, H2O)Source of chirality: d-mannono-1,4-lactone

6-Azido-6-deoxy-d-gluconic acid sodium saltC6H10N3NaO6Ee = 100%[α]D24=+7.0 (c 0.3, H2O)Source of chirality: d-glucose

6-Amino-6-deoxy-d-galactonic acidC6H13NO6Ee = 100%[α]D24=+83.2 (c 0.4, H2O)Source of chirality: d-galactono-1,4-lactone

6-Amino-6-deoxy-d-mannonic acidC6H13NO6Ee = 100%[α]D24=+4.3 (c 0.6, H2O)Source of chirality: d-mannono-1,4-lactone

6-Amino-6-deoxy-d-gluconic acidC6H13NO6Ee = 100%[α]D24=+18.7 (c 0.5, H2O)Source of chirality: d-glucose